The present invention relates to recording and reproducing method of a magnetic recording particulate medium (i.e., a coating-type magnetic recording medium), and a magnetic recording medium for use in the method, in particular, relates to recording and reproducing method of a magnetic recording medium having a thin magnetic layer for high density recording, and a magnetic recording medium for use in the method.
Along with the increase in the amount of data to be dealt with, the capacity thereof has become insufficient and the increase of the capacity of the floppy disc has been demanded.
Further, in the field of magnetic tapes, with the spread of office computers, such as minicomputers, personal computers and work stations, magnetic tapes for recording computer data as external storage media (so-called backup tapes) have been eagerly studied in recent years. For the realization of the magnetic tapes for such uses, the improvement of recording capacity has been strongly demanded conjointly with the miniaturization of a computer and the increase of information processing ability (e.g., information throughput).
Magnetic heads working with electromagnetic induction as the principle of operation (an induction type magnetic head) are conventionally used and spread. However, magnetic heads of this type are approaching their limit for use in the field of higher density recording and reproduction. That is, it is necessary to increase the number of winding of the coil of a reproduction head to obtain larger reproduction output, but when the winding number is increased, the inductance increases and the resistance at high frequency heightens, as a result, the reproduction output lowers. In recent years, reproduction heads which work with MR (magneto-resistance) as the principle of operation are proposed and come to be used in hard discs. As compared with the induction type magnetic disc, several times of reproduction output can be obtained with the MR head. Further, an induction coil is not used in the MR head, noises generated from instruments, e.g., impedance noises, are extremely reduced, therefore, it becomes possible to obtain a great S/N ratio by lowering the noise coming from magnetic recording media. In other words, good recording can be done and high density recording property can be drastically improved by lessening the noise of magnetic recording media hiding behind the instruments.
Magnetic recording particulate media (i.e., coating type magnetic recording media excellent in productivity and inexpensive and so far been used are known.
For example, a high capacity magnetic recording medium comprising a nonmagnetic layer having provided thereon a magnetic layer having a thickness of 1.0 xcexcm or less and containing an abrasive having a Mohs"" hardness of 6 or more and an average particle size of larger than the thickness of the magnetic layer is disclosed in JP-A-5-197946 (the term xe2x80x9cJP-Axe2x80x9d as used herein means an xe2x80x9cunexamined published Japanese patent applicationxe2x80x9d). Further, a high capacity magnetic recording disc comprising a nonmagnetic layer having provided thereon a magnetic layer having a thickness of 0.5 xcexcm or less and containing an abrasive having a Mohs"" hardness of 6 or more and an average particle size of from 0.8 to 1.4 times larger than the average particle size of the ferromagnetic powder, and an average particle size of from 2 to 4 times larger than the average particle size of the ferromagnetic powder is disclosed in JP-A-6-68453.
The evaluation of these magnetic recording media is in recording and reproducing using an MIG (metal-in-gap) head which is an induction type magnetic head, hence track density is relatively low and when higher density recording is done by further lessening a track width or thinning the magnetic layer thickness, a sufficient S/N ratio cannot be obtained at reproduction. In particular, the influence of the abrasive becomes large when an MR head is used, which causes the degradation of S/N ratio.
A magnetic recording and reproducing method which does not generate a noise and is excellent in a high density characteristic even when a conventionally used coating type magnetic recording medium excellent in productivity and inexpensively commercially available is combined with an MR head, and a magnetic recording medium for use in the method have been desired.
An object of the present invention is to provide a magnetic recording and reproducing method which is excellent in electromagnetic characteristics and optimal for digital recording, and a magnetic recording medium for use in the method.
The present invention has been attained by the following means:
(1) A magnetic recording and reproducing method comprising recording and reproducing a signal in a track width (A) of less than 5 xcexcm on a magnetic medium comprising a support having provided thereon a magnetic layer containing at least a ferromagnetic powder, an abrasive and a binder with a magnetic head, wherein the average longer size (B) of the abrasive particle(s) on the magnetic layer surface is ⅓ or less of the track width (A).
(2) A magnetic recording medium which is used in the magnetic recording and reproducing method as described in the above item (1), wherein the magnetic recording medium is a magnetic recording medium comprising a support having provided thereon a magnetic layer containing at least a ferromagnetic powder, an abrasive and a binder, and the average longer size (B) of the abrasive particle(s) which are present on the magnetic layer surface is ⅓ or less of the track width (A).
(3) In the magnetic recording and reproducing method and the magnetic recording medium as described in the above item (1) or (2), the magnetic recording medium comprises a support, a substantially nonmagnetic lower layer provided on the support and a magnetic layer containing a ferromagnetic metal powder or a hexagonal ferrite powder dispersed in a binder provided on the nonmagnetic lower layer, and the magnetic layer has a layer thickness of from 0.01 to 0.15 xcexcm.
(4) In the magnetic recording and reproducing method and the magnetic recording medium as described in the above item (1) or (2), the magnetic recording medium is for MR head reproduction.
The magnetic recording and reproducing method of the present invention prescribes the relationship between the average longer size (B) of the abrasive particle(s) which are present on the magnetic layer surface of the magnetic recording medium on which a signal is recorded and reproduced in a track width (A) of less than 5 xcexcm and the track width (A), and it is necessary that the relationship (B)/(A)xe2x89xa6⅓ should be satisfied, particularly (B)/(A)xe2x89xa60.20is preferred. The value of (B)/(A) is called ratio xcex1. The lower limit of ratio xcex1 is determined by the balance with other characteristics such as the size of the track width (A) and durability, but is generally 0.05 or more.
The present invention is a magnetic recording and reproducing method comprising the step of scanning the magnetic layer surface of a magnetic recording medium having the magnetic layer surface satisfying the above-described ratio xcex1 with a magnetic head while ensuring the track width satisfying the ratio xcex1, and the present invention is optimal for reproduction with an MR head.
In the present invention, the average longer size (B) of an abrasive particle(s) is determined by the following method.
The average longer size of an abrasive particle(s) is obtained by subjecting a magnetic layer surface to plasma treatment with Plasma Reactor PR41 (manufactured by Yamato Kagaku K.K.) under the condition of transmitting frequency of 13.56 MHz, output impedance of 50 ohm, output power of 20 W, degree of vacuum of 20 to 30 Pa, oxygen flow rate of 30 ml/min, and treatment time of 20 minutes, after drying, observing the abrasive particle(s) and/or clusters mainly comprising abrasives by an electron microscope of 15,000 magnifications, measuring the largest value of the width (i.e., the longer size), and taking the average value of 50 abrasive particles and/or cluster mainly comprising abrasives as the average longer size. In the present invention, a cluster mainly comprising abrasives means those derived from a plurality of abrasives coalesced in one body via a binder or abrasives and further other powders coalesced in one body via a binder, and a cluster as a whole is taken as one. The measured 50 abrasive particle (s) and/or cluster mainly comprising abrasives are preferably distributed on the surface of the magnetic layer in the ratio of from 0.5 to 1.0 xcexcm2.
The average longer size (B) of an abrasive can be arbitrarily adjusted by selecting the abrasive and the addition amount whose average particle size is well-known.
The present invention further provides a magnetic recording medium comprising the magnetic layer having an abrasive of the average longer size (B) satisfying the above-described ratio a, on the surface which is used in the magnetic recording and reproducing method of the present invention.
The magnetic recording medium is a magnetic recording medium comprising a support having provided thereon in order of a substantially nonmagnetic lower layer and a magnetic layer containing a ferromagnetic metal powder or a hexagonal ferrite powder dispersed in a binder, and the layer thickness of the magnetic layer is preferably from 0.01 to 0.15 xcexcm in view of high density recording.
The magnetic recording medium according to the present invention is described below.
Magnetic Layer
A magnetic layer may be provided on one side or may be provided on both sides of the support of the magnetic recording medium according to the present invention.
The magnetic layer provided on one side may be a monolayer (i.e., a single layer) or may be plural layers comprising different compositions. It is preferred in the present invention to provide a substantially nonmagnetic lower layer (sometimes, called a nonmagnetic layer or a lower layer) between the support and the magnetic layer. The magnetic layer may also be called an upper layer or an upper magnetic layer.
The upper magnetic layer may be coated after simultaneous or successive coating of the lower layer while the lower layer is still wet (W/W coating, wet-on-wet) or may be coated after the lower layer is dried (W/D coating, wet-on-dry). W/W coating is preferably used in view of the productivity but in the case of a disc-like medium, wet-on-dry coating can be sufficiently used. Since the upper layer and the lower layer can be formed simultaneously by W/W coating, a surface treatment step, e.g., a calendering step, can be utilized effectively and the surface roughness of the upper magnetic layer can be improved even the layer is a thin layer.
Ferromagnetic metal powders or hexagonal ferrite powders are preferably used as the ferromagnetic powder in the magnetic layer.
Ferromagnetic Metal Power
The ferromagnetic metal powders are preferably ferromagnetic metal powders mainly comprising xcex1-Fe as a main component. These ferromagnetic metal powders may contain, in addition to the prescribed atoms, the following atoms, e.g., Al, Si, Ca, Mg, Ti, Cr, Cu, Y, Sn, Sb, Ba, W, La, Ce, Pr, Nd, P, Co, Mn, Zn, Ni, Sr and B. In particular, it is preferred to contain at least one of Al, Ca, Mg, Y, Ba, La, Nd, Sn, Co and Ni, in addition to xcex1-Fe. The alloy of Co with Fe is particularly preferred to increase saturation magnetization ("sgr"s) and improve demagnetization. The content of Co is preferably from 1 to 40 atomic %, more preferably from 15 to 35 atomic %, and most preferably from 20 to 35 atomic %, the content of rare earth elements such as Y is preferably from 1.5 to 12 atomic %, more preferably from 3 to 10 atomic %, and most preferably from 4 to 9 atomic %, and the content of Al is preferably from 1.5 to 12 atomic %, more preferably from 3 to 10 atomic %, and most preferably from 4 to 9 atomic %, each based on Fe. Al and the rare earth elements including Y function as a sintering inhibitor, the combination use of them gives the excellent sintering inhibiting effect. These ferromagnetic powders may be previously treated with dispersants, lubricants, surfactants and antistatic agents before dispersion. Specifically, the examples are disclosed in JP-B-44-14090 (the term xe2x80x9cJP-Bxe2x80x9d as used herein means an xe2x80x9cexamined Japanese patent publicationxe2x80x9d), JP-B-45-18372, JP-B-47-22062, JP-B-47-22513, JP-B-46-28466, JP-B-46-38755, JP-B-47-4286, JP-B-47-12422, JP-B-47-17284, JP-B-47-18509, JP-B-47-18573, JP-B-39-10307, JP-B-46-39639, U.S. Pat. Nos. 3,026,215, 3,031,341, 3,100,194, 3,242,005, and 3,389,014.
The ferromagnetic metal powders may contain a small amount of a hydroxide or an oxide. Ferromagnetic metal powders can be prepared by well-known methods, such as a method of reducing a moisture-containing iron oxide having been subjected to sintering inhibiting treatment or an iron oxide with a reducing gas, e.g., hydrogen, to thereby obtain Fe or Fexe2x80x94Co particles; a method of reducing a composite organic acid salt (mainly an oxalate) with a reducing gas, e.g., hydrogen; a method of heat decomposing a metal carbonyl compound; a method of adding to an aqueous solution of a ferromagnetic metal a reducing agent, e.g., sodium boron hydride, hypophosphite or hydrazine, to effect reduction; and a method of evaporating a metal in a low pressure inert gas to obtain a powder. The thus-obtained ferromagnetic metal powders are subjected to well-known gradual oxidation treatment. A method of forming oxide films on the surfaces of ferromagnetic metal powders by reducing a moisture-containing iron oxide or an iron oxide with a reducing gas, e.g., hydrogen, and regulating partial pressures of an oxygen-containing gas and an inert gas, temperature and time is less in demagnetization and preferably used in the present invention.
The ferromagnetic metal powders for use in the magnetic layer in the present invention have a specific surface area (SBET) as measured by the BET method of from 40 to 80 m2/g, preferably from 45 to 70 m2/g. When SBET is less than 40 m2/g, noise increases and when more than 80 m2/g, smooth surface is obtained with difficulty, which is not preferred. The ferromagnetic metal powders for use in the magnetic layer according to the present invention have a crystallite size of generally from 80 to 180 xc3x85, preferably from 100 to 170 xc3x85, and more preferably from 110 to 165 xc3x85. The average long axis length of the ferromagnetic metal powders is generally from 0.02 to 0.25 xcexcm, preferably from 0.03 to 0.15 xcexcm, and more preferably from 0.03 to 0.12 xcexcm. The ferromagnetic metal powders preferably have an average acicular ratio (the average of (long axis length/short axis length)) of from 3 to 15, more preferably from 3 to 10. The ferromagnetic metal powders have a saturation magnetization ("sgr"s) of generally from 90 to 170 Axc2x7m2/kg, preferably from 100 to 160 Axc2x7m2/kg, and more preferably from 110 to 160 Axc2x7m2/kg. The ferromagnetic metal powders have a coercive force of preferably from 135 to 279 kA/m, and more preferably from 143 to 239 kA/m.
The ferromagnetic metal powders preferably have a water content of from 0.1 to 2 mass % (i.e., weight %). The water content of the ferromagnetic metal powders is preferably optimized by selecting the kinds of binders. The pH of the ferromagnetic metal powders is preferably optimized by the combination with the binder to be used. The pH range is from 6 to 12, preferably from 7 to 11. The SA (stearic acid) adsorption amount of the ferromagnetic metal powders (the standard of the basic point of the surface) is from 1 to 15 xcexcmol/m2, preferably from 2 to 10 xcexcmol/m2, and more preferably from 3 to 8 xcexcmol/m2. When a ferromagnetic metal powder high in a stearic acid adsorption amount is used, it is preferred to manufacture a magnetic recording medium by modifying the surface of the ferromagnetic metal powder with organic substances which are strongly adsorbed onto the surface. Soluble inorganic ions (e.g., Na, Ca, Fe, Ni, Sr, NH4, SO4, Cl, NO2 and NO3) are sometimes contained in the ferromagnetic metal powders. It is preferred substantially not to contain such soluble inorganic ions but the properties of the ferromagnetic metal powders are not particularly affected if the total content of each ion is 300 ppm or less or so. The ferromagnetic metal powders for use in the present invention preferably have less voids and the value thereof is 20% by volume or less, more preferably 5% by volume or less. The shape of the ferromagnetic metal powders is not particularly restricted, and any shape such as an acicular shape, an ellipsoidal shape or a spindle shape may be used so long as the above-described particle sizes and magnetic characteristics are satisfied. Switching field distribution (SFD) of the ferromagnetic metal powders themselves is preferably small. It is necessary to make Hc distribution of the ferromagnetic metal powders narrow. When the SFD is small, reversal of magnetization becomes sharp and peak shift is less, which is therefore, suitable for high density digital magnetic recording. For achieving small Hc distribution, making particle size distribution of goethite in the ferromagnetic metal powders good, using monodispersed xcex1-Fe2O3 and preventing sintering among particles are effective methods.
Hexagonal Ferrite Powder
The examples of the hexagonal ferrite for use in the magnetic layer according to the present invention include substitution products of barium ferrite, strontium ferrite, lead ferrite and calcium ferrite, and substitutes of their ferrites. Specifically, barium ferrite and strontium ferrite of magnetoplumbite type, magnetoplumbite type ferrite having covered the particle surfaces with spinel, and barium ferrite and strontium ferrite of magnetoplumbite type partially containing spinel phase are exemplified. The hexagonal ferrite powders may contain, in addition to the prescribed atoms, the following atoms, e.g., Al, Si, S, Sc, Ti, V, Cr, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, W, Re, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, P, Co, Mn, Zn, Ni, Sr, B, Ge and Nb. In general, the hexagonal ferrite powders containing the following elements can be used, e.g., Coxe2x80x94Zn, Coxe2x80x94Ti, Coxe2x80x94Tixe2x80x94Zr, Coxe2x80x94Tixe2x80x94Zn, Nixe2x80x94Tixe2x80x94Zn, Nbxe2x80x94Znxe2x80x94Co, Sbxe2x80x94Znxe2x80x94Co, and Nbxe2x80x94Zn. According to starting materials and producing processes, specific impurities may be contained.
The average tabular diameter of the hexagonal ferrite powders for use in the present invention is generally from 10 to 50 nm, preferably from 10 to 40 nm, and particularly preferably from 10 to 35 nm, although it varies according to recording density. The tabular diameter used here means the longest hexagonal diameter of the base of a hexagonal pole of a hexagonal ferrite magnetic powder, and the average tabular diameter is the arithmetic mean of it.
When reproduction is performed using a magneto-resistance head particularly for increasing track density, it is necessary to reduce noise, accordingly the tabular diameter is preferably 35 nm or less, but when the tabular diameter is smaller than 10 nm, stable magnetization cannot be obtained due to thermal fluctuation. While when the tabular diameter exceeds 50 nm, noise increases, therefore, none of such tabular diameters are suitable for high density recording. A tabular ratio (tabular diameter/tabular thickness) is preferably from 1 to 15, more preferably from 1 to 7. When a tabular ratio is small, the packing density in a magnetic layer becomes high, which is preferred but sufficient orientation cannot be obtained.
When a tabular ratio is more than 15, noise increases due to stacking among particles. The specific surface area (SBET) measured by the BET method of the particles having diameters within this range is generally from 30 to 200 m2/g. The specific surface areas nearly coincide with the values obtained by arithmetic operations from tabular diameters and tabular thicknesses. The distribution of tabular diameter/tabular thickness is in general preferably as narrow as possible. It is difficult to show specific surface area distributions in numerical values but distributions can be compared by measuring TEM photographs of 500 particles selected randomly. The distribution is in many cases not regular distribution, but when expressed by the standard deviation to the average diameter by computation, a/average diameter is from 0.1 to 2.0. For obtaining narrow particle size distribution, it is efficient to make a particle-forming reaction system homogeneous to the utmost, particles formed are subjected to distribution-improving treatments as well. For example, a method of selectively dissolving ultrafine particles in an acid solution is also known. Coercive force (Hc) of generally from about 500 to about 5,000 Oe (=about 40 to 400 kA/m) measured in magnetic powders can be produced. Higher Hc is advantageous for high density recording but it is restricted by the capacities of recording heads. Hc can be controlled by particle diameters (tabular diameter/tabular thickness), the kinds and amounts of elements contained, the substitution sites of elements, and the reaction conditions of particle formation. Saturation magnetization ("sgr"s) is from 30 to 80 Axc2x7m2/kg. "sgr"s has the inclination of becoming smaller as particles become finer. For the improvement thereof, a method of reducing the crystallization temperature or heat treatment temperature and time, a method of increasing the amount of the compound to be added, or a method of increasing the surface treating amount may be used. A W-type hexagonal ferrite can also be used. Further, when magnetic powders are dispersed, particle surfaces of magnetic powders may be treated with substances compatible with the dispersion media and the polymers. Inorganic or organic compounds are used as a surface treating agent. For example, oxides or hydroxides of Si, Al and P, various kinds of silane coupling agents, and various kinds of titanium coupling agents are representative examples. The amount of these surface treating agents is from 0.1 to 10% based on the amount of the magnetic powder. The pH of magnetic powders is also important for dispersion, and is in general from 4 to 12. The optimal value is dependent upon the dispersion medium and the polymer. Taking the chemical stability and the storage stability of magnetic media into consideration, pH of from 6 to 11 or so is selected. The water content in the magnetic powder also affects dispersion. The optimal value is dependent upon the dispersion medium and the polymer, and the water content of from 0.01 to 2.0% is selected in general. Hexagonal ferrite powders can be produced by (1) a glass crystallization method of mixing a metallic oxide which substitutes barium oxide, iron oxide and iron, and a boron oxide as a glass-forming material, so as to make a desired ferrite composition, melting and quenching to obtain an amorphous product, reheat-treating the obtained product, washing and then pulverizing, to thereby obtain a barium ferrite crystal powder, (2) a hydrothermal reaction method of neutralizing a solution of barium ferrite composition metal salt with an alkali, removing the byproducts, heating liquid phase at 100xc2x0 C. or more, washing, drying and pulverizing, to thereby obtain a barium ferrite crystal powder, and (3) a coprecipitation method of neutralizing a solution of barium ferrite composition metal salt with an alkali, removing the byproducts, drying, treating at 1,100xc2x0 C. or less, and then pulverizing, to thereby obtain a barium ferrite crystal powder, and any of these methods can be sued in the present invention.
Lower Layer
The lower layer is described in detail below. The lower layer preferably comprises a nonmagnetic inorganic powder and a binder as main components. The nonmagnetic inorganic powder for use in the lower layer can be selected from inorganic compounds, e.g., metallic oxide, metallic carbonate, metallic sulfate, metallic nitride, metallic carbide, metallic sulfide, etc. The examples of inorganic compounds are selected from the following compounds and they can be used alone or in combination, e.g., xcex1-alumina having an alpha-conversion rate of 90% or more, xcex2-alumina, xcex3-alumina, xcex8-alumina, silicon carbide, chromium oxide, cerium oxide, xcex1-iron oxide, hematite, goethite, corundum, siliconnitride, titanium carbide, titanium oxide, silicon dioxide, tin oxide, magnesium oxide, tungsten oxide, zirconium oxide, boron nitride, zinc oxide, calcium carbonate, calcium sulfate, barium sulfate, and molybdenum disulfide. Of these compounds, titanium dioxide, zinc oxide, iron oxide and barium sulfate are particularly preferred because they have small particle size distribution and various means for imparting functions, and titanium dioxide and xcex1-iron oxide are more preferred. These nonmagnetic inorganic powders preferably have an average particle size of from 0.005 to 2 xcexcm.
If necessary, a plurality of nonmagnetic inorganic powders each having a different particle size may be combined, or a single nonmagnetic inorganic powder may have broad particle size distribution so as to attain the same effect as such a combination. These nonmagnetic inorganic powders particularly preferably have an average particle size of from 0.01 to 0.2 xcexcm.
In particular, when the nonmagnetic inorganic powder is a granular metallic oxide, the average particle size thereof is preferably 0.08 xcexcm or less, and when the nonmagnetic inorganic powder is an acicular metallic oxide, the average long axis length thereof is preferably 0.3 xcexcm or less, more preferably 0.2 xcexcm or less. The Nonmagnetic inorganic powders for use in the present invention have a tap density of from 0.05 to 2 g/ml, preferably from 0.2 to 1.5 g/ml; a water content of generally from 0.1 to 5 mass % (i.e., weight %), preferably from 0.2 to 3 mass %, and more preferably from 0.3 to 1.5 mass %; a pH value of from 2 to 11, and particularly preferably between 5.5 and 10; a specific surface area (SBET) of from 1 to 100 m2/g, preferably from 5 to 80 m2/g, and more preferably from 10 to 70 m2/g; a crystallite size of from 0.004 to 1 xcexcm, and more preferably from 0.04 to 0.1 xcexcm; an oil absorption amount using DBP (dibutyl phthalate) of from 5 to 100 ml/100 g, preferably from 10 to 80 ml/100 g, and more preferably from 20 to 60 ml/100 g; and a specific gravity of from 1 to 12, and preferably from 3 to 6. The shape of the nonmagnetic inorganic powders may be any of an acicular, spherical, polyhedral, or tabular shape. The nonmagnetic inorganic powders preferably have a Mohs"" hardness of from 4 to 10. The SA (stearic acid) adsorption amount of the nonmagnetic inorganic powders is from 1 to 20 xcexcmol/m2, preferably from 2 to 15 xcexcmol/m2, and more preferably from 3 to 8 xcexcmol/m2. The pH of the nonmagnetic inorganic powders is preferably between 3 and 6. The surfaces of these nonmagnetic inorganic powders are preferably covered with Al2O3, SiO2, TiO2, ZrO2, SnO2, Sb2O3, ZnO or Y2O3. Al2O3, SiO2, TiO2 and ZrO2 are particularly preferred in the point of dispersibility, and Al2O3, SiO2 and ZrO2 are more preferred. They can be used in combination or may be used alone. A method in which the surface treatment may be performed by coprecipitation, alternatively, surface treatment of particles may be previously performed to be covered with alumina in the first place, then the alumina-covered surface is covered with silica, or vice versa, according to purposes. The surface-covering layer may be porous layer, if necessary, but a homogeneous and dense surface is generally preferred.
The specific examples of the nonmagnetic inorganic powders for use in the lower layer in the present invention and the producing methods are disclosed in WO 98/35345.
By the addition of carbon blacks to the lower layer, a desired micro Vickers"" hardness can be obtained, surface electrical resistance (Rs) and light transmittance can be reduced as well, as are well-known effects. It is also possible to bring about the effect of stocking a lubricant by the addition of carbon blacks to the lower layer. Furnace blacks for rubbers, thermal blacks for rubbers, carbon blacks for coloring and acetylene blacks can be used as carbon blacks. Carbon blacks for use in the lower layer should optimize the following characteristics by the desired effects and sometimes more effects can be obtained by the combined use.
Carbon blacks for use in the lower layer according to the present invention have a specific surface area (SBET) of generally from 100 to 500 m2/g, preferably from 150 to 400 m2/g, a DBP oil absorption amount of generally from 20 to 400 ml/100 g, preferably from 30 to 400 ml/100 g, an average particle size of generally from 5 to 80 nm, preferably from 10 to 50 nm, and more preferably from 10 to 40 nm, and a small amount of carbon blacks having an average particle size of larger than 80 nm may be contained in the lower layer. Carbon blacks for use in the lower layer have pH of from 2 to 10, a water content of from 0.1 to 10%, and a tap density of from 0.1 to 1 g/ml.
The specific examples of the carbon blacks for use in the lower layer in the present invention are disclosed in WO 98/35345. Carbon blacks can be used within the range not exceeding 50 mass % based on the above nonmagnetic inorganic powders (exclusive of carbon blacks) and not exceeding 40 mass % based on the total mass (i.e., the total weight) of the nonmagnetic layer. These carbon blacks can be used alone or in combination. Regarding the carbon blacks which can be used in the present invention, e.g., the disclosure in Carbon Black Binran (Handbook of Carbon Blacks), compiled by Carbon Black Kyokai can be referred to.
Organic powders can be used in the lower layer according to purposes. The examples of organic powders include an acryl styrene resin powder, a benzoguanamine resin powder, a melamine resin powder, and a phthalocyanine pigment. In addition, a polyolefin resin powder, a polyester resin powder, a polyamide resin powder, a polyimide resin powder, and a polyethylene fluoride resin powder can also be used. The producing methods of these organic powders are disclosed in JP-A-62-18564 and JP-A-60-255827.
The binder resins, lubricants, dispersants, additives, solvents, dispersing methods, and others used for the magnetic layer described below can be used in the lower layer and the backing layer described later. In particular, with respect to the amounts and the kinds of binder resins, additives, the amounts and the kinds of dispersants, well-known prior art techniques regarding the magnetic layer can be applied to the lower layer.
Binder
Conventionally well-known thermoplastic resins, thermosetting resins, reactive resins and mixtures of these resins are used as a binder in the present invention.
Thermoplastic resins having a glass transition temperature of from xe2x88x92100 to 150xc2x0 C., a number average molecular weight of from 1,000 to 200,000, preferably from 10,000 to 100,000, and a polymerization degree of from about 50 to about 1,000 can be used in the present invention.
The examples of thermoplastic resins include polymers or copolymers containing, as the constituting unit, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylate, vinylidene chloride, acrylonitrile, methacrylic acid, methacrylate, styrene, butadiene, ethylene, vinyl butyral, vinyl acetal or vinyl ether; polyurethane resins and various rubber resins. The examples of thermosetting resins and reactive resins include phenolic resins, epoxy resins, curable type polyurethane resins, urea resins, melamine resins, alkyd resins, acrylic reactive resins, formaldehyde resins, silicone resins, epoxy-polyamide resins, mixtures of polyester resins and isocyanate prepolymers, mixtures of polyesterpolyol and polyisocyanate, and mixtures of polyurethane and polyisocyanate. These resins are described in detail in Plastic Handbook, Asakura Shoten. It is also possible to use well-known electron beam curable type resins in each layer. The examples of these resins and producing methods are disclosed in detail in JP-A-62-256219. These resins can be used alone or may be used in combination. The examples of preferred combinations include at least one resin selected from vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-vinyl alcohol copolymers, and vinyl chloride-vinyl acetate-maleic anhydride copolymers with polyurethane resins, or combinations of these resins with polyisocyanate.
As the polyurethane resins, those having well-known structures, e.g., polyester polyurethane, polyether polyurethane, polyether polyester polyurethane, polycarbonate polyurethane, polyester polycarbonate polyurethane, and polycaprolactone polyurethane can be used. For the purpose of further improving the dispersibility and the durability, it is referred that at least one polar group selected from the following groups is introduced by copolymerization or addition reaction, with respect to all of the above binders, e.g., xe2x80x94COOM, xe2x80x94SO3M, xe2x80x94OSO3M, xe2x80x94Pxe2x95x90O(OM)2, xe2x80x94Oxe2x80x94Pxe2x95x90O(OM)2 (wherein M represents a hydrogen atom or an alkali metal salt group), xe2x80x94NR2, xe2x80x94N+R3 (R represents a hydrocarbon group), an epoxy group, xe2x80x94SH, or xe2x80x94CN. The content of the polar group is from 10xe2x88x921 to 10xe2x88x928 mol/g, preferably from 10xe2x88x922 to 10xe2x88x926 mol/g. It is preferred that polyurethane resins have at least one OH group at each terminal of a polyurethane molecule, i.e., two or more in total, besides the above polar groups. As OH groups form three dimensional network structure by crosslinking with a polyisocyanate curing agent, they are preferably contained in a molecule as many as possible. In particular, it is preferred that OH groups are present at terminals of a molecule, since the reactivity with the curing agent becomes high. It is preferred for polyurethane to have 3 or more OH groups, particularly preferably 4 or more OH groups, at terminals of a molecule. When polyurethane is used in the present invention, the polyurethane has a glass transition temperature of generally from xe2x88x9250 to 150xc2x0 C., preferably from 0 to 100xc2x0 C., and particularly preferably from 30 to 100xc2x0 C., breaking extension of from 100 to 2,000%, breaking stress of generally from 0.05 to 10 kg/nm2 (=about 0.49 to 98 MPa), and a yielding point of from 0.05 to 10 kg/mm2 (=about 0.49 to 98 MPa). Due to these physical properties, a coated film having good mechanical properties can be obtained.
The specific examples of the binders for use in the present invention include VAGH, VYHH, VMCH, VAGF, VAGD, VROH, VYES, VYNC, VMCC, XYHL, XYSG, PKHH, PKHJ, PKHC and PKFE (manufactured by Union Carbide Co., Ltd.), MPR-TA, MPR-TA5, MPR-TAL, MPR-TSN, MPR-TMF, MPR-TS, MPR-TM and MPR-TAO (manufactured by Nisshin Chemical Industry Co., Ltd.), 1000W, DX80, DX81, DX82, DX83 and 100FD (manufactured by Electro Chemical Industry Co., Ltd.), MR-104, MR-105, MR-110, MR-100, MR-555 and 400X-110A (manufactured by Nippon Zeon Co., Ltd.) as vinyl chloride copolymers; Nippollan N2301, N2302 and N2304 (manufactured by Nippon Polyurethane Co., Ltd.), Pandex T-5105, T-R3080, T-5201, Burnock D-400, D-210-80, Crisvon 6109 and 7209 (manufactured by Dainippon Chemicals and Ink. Co., Ltd.), Vylon UR8200, UR8300, UR8700, RV530 and RV280 (manufactured by Toyobo Co., Ltd.), polycarbonate polyurethane, Daipheramine 4020, 5020, 5100, 5300, 9020, 9022 and 7020 (manufactured by Dainichi Seika K.K.), polyurethane, MX5004 (manufactured by Mitsubishi Kasei Corp.), polyurethane, Sunprene SP-150 (manufactured by Sanyo Chemical Industries Co. Ltd.), polyurethane, Salan F310 and F210 (manufactured by Asahi Chemical Industry Co., Ltd.) as polyurethane resins, etc.
The amount of the binder for use in the nonmagnetic layer and the magnetic layer according to the present invention is from 5 to 50 mass % (i.e., weight %), preferably from 10 to 30 mass %, based on the weight of the nonmagnetic inorganic powder or the magnetic powder respectively. When vinyl chloride resins are used, the amount thereof is from 5 to 30 mass %, when polyurethane resins are used, the amount thereof is from 2 to 20 mass %, and polyisocyanate is preferably used in an amount of from 2 to 20 mass % in combination, however, for instance, when the corrosion of a head is caused by a slight amount of chlorine due to dechlorination, it is possible to use polyurethane alone or a combination of polyurethane and isocyanate.
When the magnetic recording medium according to the present invention comprise two or more layers, the amount of the binder, the amounts of the vinyl chloride resin, polyurethane resin, polyisocyanate or other resins contained in the binder, the molecular weight of each resin constituting the magnetic layer, the amount of polar groups, or the above-described physical properties of resins can of course be varied in the nonmagnetic layer and the magnetic layer, according to necessity. These factors should be rather optimized in respective layers. Well-known techniques with respect to multilayer magnetic layers can be used in the present invention. For example, when the amount of the binder is varied in each layer, it is effective to increase the amount of the binder contained in the magnetic layer to reduce scratches on the surface of the magnetic layer. For improving the head touch against the head, it is effective to increase the amount of the binder in the nonmagnetic layer to impart flexibility.
The examples of the polyisocyanates for use in the present invention include isocyanates, e.g., tolylenediisocyanate, 4,4xe2x80x2-diphenylmethanediisocyanate, hexamethylenediisocyanate, xylylenediisocyanate, naphthylene-1,5-diisocyanate, o-toluidinediisocyanate, isophoronediisocyanate, and triphenylmethanetriisocyanate; reaction products of these isocyanates with polyalcohols; and polyisocyanates formed by condensation reaction of isocyanates. These polyisocyanates are commercially available under the trade names of Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR and Millionate MTL (manufactured by Nippon Polyurethane Co., Ltd.), Takenate D-102, Takenate D-110N, Takenate D-200 and Takenate D-202 (manufactured by Takeda Chemical Industries, Ltd.), and Desmodur L, Desmodur IL, Desmodur N and Desmodur HL (manufactured by Sumitomo Bayer Co., Ltd.). These polyisocyanates may be used alone or in combinations of two or more thereof in each layer, taking advantage of a difference in curing reactivity.
Carbon Black, Abrasive
The carbon blacks for use in the magnetic layer according to the present invention include furnace blacks for rubbers, thermal blacks for rubbers, carbon blacks for coloring, and acetylene blacks. Carbon blacks for use in the magnetic layer of the present invention preferably have a specific surface area (SBET) of from 5 to 500 m2/g, a DBP oil absorption amount of from 10 to 400 ml/100 g, an average particle size of from 5 to 300 nm, pH of from 2 to 10, a water content of from 0.1 to 10%, and a tap density of from 0.1 to 1 g/ml. The specific examples of the carbon blacks for use in the magnetic layer of the present invention are disclosed in WO 98/35345.
Carbon blacks can serve various functions such as preventing static charges of the magnetic layer, reducing a friction coefficient, imparting a light-shielding property and improving a film strength. Such functions vary depending upon the kind of carbon blacks to be used. Accordingly, when the present invention takes a multilayer structure, it is of course possible to select and determine the kinds, the amounts and the combinations of the carbon blacks to be added to each layer on the basis of the above-described various properties such as the particle size, the oil absorption amount, the electroconductivity and the pH value, or these should be rather optimized in respective layers.
An abrasive can be used in the magnetic layer according to the present invention. Well-known materials essentially having a Mohs"" hardness of 6 or more are used alone or in combination as the abrasive in the magnetic layer according to the present invention. The examples of such abrasives include xcex1-alumina having an alpha-conversion rate of 90% or more, xcex2-alumina, silicon carbide, chromium oxide, cerium oxide, xcex1-iron oxide, corundum, artificial diamond, silicon nitride, silicon carbide, titanium carbide, titanium oxide, silicon dioxide, and boron nitride. The composites composed of these abrasives (abrasives obtained by surface-treating with other abrasives) may also be used. Compounds or elements other than the main component are often contained in these abrasives, but the intended effect can be attained so far as the content of the main component is 90% or more. The abrasives preferably have an average particle size of from 0.01 to 2 xcexcm and, in particular, for improving electromagnetic characteristics, abrasives having narrow particle size distribution are preferred. For improving durability, a plurality of abrasives each having a different particle size maybe combined according to necessity, or a single abrasive having a broad particle size distribution may be used so as to attain the same effect as such a combination. Preferably, the abrasives for use in the present invention have a tap density of from 0.3 to 2 g/ml, a water content of from 0.1 to 5%, a pH value of from 2 to 11 and a specific surface area (SBET) of from 1 to 30 m2/g. The shape of the abrasives for use in the present invention maybe any of acicular, spherical and die-like shapes. Preferably, the abrasive has a shape partly with edges, because a high abrasive property can be obtained. The specific examples of the abrasives for use in the magnetic layer of the present invention are disclosed in WO 98/35345 and, above all, it is effective to use diamond fine particles in the manner as disclosed in the patent for improving running durability and electromagnetic characteristics. The particle size and the amount of the abrasive to be added to a magnetic layer and a nonmagnetic layer should be selected independently at optimal values.
Additive
As the additives for use in the magnetic layer and the nonmagnetic layer of the present invention, those having a lubricating effect, an antistatic effect, a dispersing effect and a plasticizing effect are used, and by combining the additives, comprehensive improvement of capacities can be contrived. As the additives having a lubricating effect, lubricants giving remarkable action on agglutination caused by the friction of surfaces of materials with each other are used. Lubricants are classified into two types. Lubricants which are used for a magnetic recording medium cannot be judged completely whether they show fluid lubrication or boundary lubrication, but according to general concepts they are classified into higher fatty acid esters, liquid paraffins and silicon derivatives which show fluid lubrication, and long chain fatty acids, fluorine surfactants and fluorine-containing high polymers which show boundary lubrication. In a coating type magnetic recording medium, lubricants exist in a state dispersed in a binder or in a state partly adsorbed onto the surface of a ferromagnetic powder, and they migrate to the surface of a magnetic layer. The speed of migration depends upon whether the compatibility of the binder and the lubricant is good or bad. The speed of migration is slow when the compatibility of the binder and the lubricant is good and the migration speed is fast when the compatibility is bad. As one idea as to good or bad of the compatibility, there is a means of comparison of dissolution parameters of the binder and the lubricant. A nonpolar lubricant is effective for fluid lubrication and a polar lubricant is effective for boundary lubrication.
In the present invention, it is preferred to use a higher fatty acid ester showing fluid lubrication and a long chain fatty acid showing boundary lubrication each having different characteristics in combination, and it is more preferred to combine at least three of these lubricants. Solid lubricants can also be used in combination with them.
The examples of the solid lubricants which can be used in the present invention include molybdenum disulfide, tungsten graphite disulfide, boron nitride, and fluorinated graphite. The examples of the long chain fatty acids showing boundary lubrication include monobasic fatty acids having from 10 to 24 carbon atoms (which may contain an unsaturated bond or may be branched) and metal salt of these monobasic fatty acids (e.g., with Li, Na, K or Cu). The examples of the fluorine surfactants and fluorine-containing high polymers include fluorine-containing silicones, fluorine-containing alcohols, fluorine-containing esters, fluorine-containing alkyl sulfates and alkali metal salts of them. The examples of the higher fatty acid esters showing fluid lubrication include fatty acid monoesters, fatty acid diesters or fatty acid triesters composed of a monobasic fatty acid having from 10 to 24 carbon atoms (which may contain an unsaturated bond or may be branched) and any one of mono-, di-, tri-, tetra-, penta- and hexa-alcohols having from 2 to 12 carbon atoms (which may contain an unsaturated bond or may be branched), and fatty acid esters of monoalkyl ethers of alkylene oxide polymers. In addition to the above, the examples further include liquid paraffins, and as the silicon derivatives, silicone oils, e.g., dialkylpolysiloxane (the alkyl group has from 1 to 5 carbon atoms), dialkoxypolysiloxane (the alkoxy group has from 1 to 4 carbon atoms), monoalkylmonoalkoxypolysiloxane (the alkyl group has from 1 to 5 carbon atoms and the alkoxy group has from 1 to 4 carbon atoms), phenylpolysiloxane, and fluoroalkylpolysiloxane (the alkyl group has from 1 to 5 carbon atoms), silicones having a polar group, fatty acid-modified silicones, and fluorine-containing silicones.
The examples of other lubricants which can be used in the present invention include alcohols such as mono-, di-, tri-, tetra-, penta- or hexa-alcohols having from 12 to 22 carbon atoms (which may contain an unsaturated bond or may be branched), alkoxy alcohols having from 12 to 22 carbon atoms (which may contain an unsaturated bond or may be branched), and fluorine-containing alcohols, polyethylene waxes, polyolefins such as polypropylenes, ethylene glycols, polyglycols such as polyethylene oxide waxes, alkyl phosphates and alkali metal salts of alkyl phosphates, alkyl sulfates and alkali metal salts of alkyl sulfates, polyphenyl ethers, fatty acid amides having from 8 to 22 carbon atoms, and aliphatic amines having from 8 to 22 carbon atoms.
The examples of the additives having an antistatic effect, a dispersing effect and a plasticizing effect which can be used in the present invention include phenylphosphonic acids, specifically xe2x80x9cPPAxe2x80x9d (manufactured by Nissan Chemical Industries, Ltd.), etc., xcex1-naphthylphosphoric acids, phenylphosphoric acids, diphenylphosphoric acids, p-ethylbenzenephosphonic acids, phenylphosphinic acids, aminoquinones, various kinds of silane coupling agents, titanium coupling agents, fluorine-containing alkyl sulfates and alkali metal salts thereof.
The lubricants particularly preferably used in the present invention are fatty acids and fatty acid esters, and the specific examples of the lubricants are disclosed in WO 98/35345. Besides the above, other different lubricants and additives can be used in combination as well.
Additionally, nonionic surfactants, e.g., alkylene oxides, glycerols, glycidols and alkylphenol-ethylene oxide adducts; cationic surfactants, e.g., cyclic amines, ester amides, quaternary ammonium salts, hydantoin derivatives, heterocyclic compounds, phosphoniums and sulfoniums; anionic surfactants containing an acidic group, e.g., carboxylic acid, sulfonic acid, phosphoric acid, sulfate groups or phosphate groups; and amphoteric surfactants, e.g., amino acids, aminosulfonic acids, sulfates or phosphates of amino alcohols, and alkylbetains can also be used. The details of these surfactants are described in Kaimen Kasseizai Binran (Handbook of Surfactants) (published by Sangyo Tosho Co., Ltd.). These lubricants and antistatic agents may not always be 100% pure and may contain impurities such as isomers, non-reacted products, byproducts, decomposed products and oxides, in addition to the main component. However, the content of such impurities is preferably 30% or less, more preferably 10% or less.
As described in WO 98/35345, it is also preferred to use a monoester and a diester in combination as the fatty acid ester.
The surface of the magnetic layer of the magnetic recording medium in the present invention, in particular, the disc-like magnetic recording medium, has a C/Fe peak ratio of preferably from 5 to 100, particularly preferably from 5 to 80 when measured by the Auger electron spectroscopic analysis. The measuring condition of the C/Fe peak ratio by the Auger electron spectroscopic analysis is as follows.
Apparatus: Model PHI-660 manufactured by "PHgr" Co.
Measuring condition:
Primary electron beam accelerating voltage: 3 KV
Electric current of sample: 130 nA
Magnification: 250-fold
Inclination angle: 30xc2x0
The value of C/Fe peak is obtained as the C/Fe ratio by integrating the values obtained under the above conditions in the region of kinetic energy of 130 eV to 730 eV three times and finding the strengths of KLL peak of the carbon and LMM peak of the iron as differentials.
The amount of the lubricants contained in each of the upper layer and the lower layer of the magnetic recording medium according to the present invention is from 5 to 30 mass parts (i.e., weight parts) per 100 mass parts of the ferromagnetic powder or nonmagnetic inorganic powder.
The lubricants and surfactants for use in the present invention respectively have different physical functions. The kinds, amounts and proportions of generating synergistic effect of these lubricants should be determined optimally in accordance with the purpose. The nonmagnetic layer and the magnetic layer can separately contain different fatty acids each having a different melting point so as to prevent bleeding out of the fatty acids to the surface, or different esters each having a different boiling point, a different melting point or a different polarity so as to prevent bleeding out of the esters to the surface. Also, the amount of the surfactant is controlled so as to improve the coating stability, or the amount of the lubricant in the intermediate layer is made larger so as to improve the lubricating effect. Examples are by no means limited thereto. In general, the total amount of the lubricants is from 0.1 to 50 mass %, preferably from 2 to 25 mass %, based on the magnetic powder or the nonmagnetic inorganic powder.
All or a part of the additives to be used in the present invention may be added to the magnetic coating solution or the nonmagnetic coating solution in any step of the preparation. For example, the additives may be blended with the magnetic powder before the kneading step, may be added in the step of kneading the magnetic powder, the binder and the solvent, may be added in the dispersing step, may be added after the dispersing step, or may be added just before coating. According to the purpose, there is the case of capable of attaining the object by coating all or a part of the additives simultaneously with or successively after the coating of the magnetic layer. According to the purpose, the lubricants may be coated on the surface of the magnetic layer after the calendering treatment or after the completion of slitting.
Layer Structure
The thickness of the support of the magnetic recording medium in the present invention is generally from 2 to 100 xcexcm, preferably from 2 to 80 xcexcm. The thickness of the support of a computer tape is from 3.0 to 6.5 xcexcm, preferably from 3.0 to 6.0 xcexcm, and more preferably from 4.0 to 5.5 xcexcm.
An undercoating layer may be provided between the support, preferably the nonmagnetic flexible support, and the nonmagnetic or magnetic layer for adhesion improvement. The thickness of the undercoating layer is from 0.01 to 0.5 xcexcm, preferably from 0.02 to 0.5 xcexcm.
A backing layer may be provided on the side of the support opposite to the side having the magnetic layer for the purpose of providing static charge prevention and curling correction. The thickness of the backing layer is from 0.1 to 4 xcexcm, preferably from 0.3 to 2.0 xcexcm. Well-known undercoat layers and backing layers can be used for this purpose.
The thickness of the magnetic layer of the constitution comprising the lower layer and the upper layer in the present invention is optimized according to the saturation magnetization amount of the head to be used, the head gap length, and the recording signal zone, and is generally from 0.05 to 0.5 xcexcm, preferably from 0.05 to 0.30 xcexcm. The thickness of the lower nonmagnetic layer is generally from 0.2 to 5.0 xcexcm, preferably from 0.3 to 3.0 xcexcm, and more preferably from 1.0 to 2.5 xcexcm. The lower layer exhibits the effect of the present invention so long as it is substantially a nonmagnetic layer even if, or intendedly, it contains a small amount of a magnetic powder as an impurity, which is as a matter of course regarded as essentially the same constitution as in the present invention. The term xe2x80x9csubstantially a nonmagnetic layerxe2x80x9d means that the residual magnetic flux density of the lower layer is 100 mT or less and the coercive force of the lower layer is 100 Oe (=about 8 kA/m) or less, preferably the residual magnetic flux density and the coercive force are zero. When the lower layer contains a magnetic powder, the content of the magnetic layer is preferably less than xc2xd of the entire inorganic powder contained in the lower layer. As the lower layer, a soft magnetic layer containing a soft magnetic powder and a binder may be formed in place of the nonmagnetic layer. The thickness of the soft magnetic layer is the same as the thickness of the lower layer described above.
When the magnetic recording medium in the present invention has two magnetic layers, the nonmagnetic layer and the soft magnetic layer may be or may not be formed, for example, the thickness of the magnetic layer farther from the support can be from 0.2 to 2 xcexcm, preferably from 0.2 to 1.5 xcexcm, and the thickness of the magnetic layer nearer from the support can be from 0.8 to 3 xcexcm. When the magnetic layer consists of a single layer, the thickness is generally from 0.2 to 5 xcexcm, preferably from 0.5 to 3 xcexcm, and more preferably from 0.5 to 1.5 xcexcm.
Backing Layer
The magnetic recording medium in the present invention can be provided with a backing layer. A magnetic disc may also be provided with a backing layer, however, in general, a magnetic tape for a computer data recording is decidedly required to have an excellent repeating-running property as compared with a video tape and an audio tape. For maintaining such a high running durability, it is preferred for the backing layer to contain a carbon black and an inorganic powder.
Two kinds of carbon blacks respectively having different average particle sizes are preferably used in combination. In such a case, it is preferred to use a fine carbon black having an average particle size of from 10 to 20 nm and a coarse carbon black having an average particle size of from 230 to 300 nm in combination. In general, by the addition of a fine carbon black as above, the surface electrical resistance of the backing layer and light transmittance can be set up at low values. Since there are many kinds of magnetic recording apparatus making use of light transmittance of a tape to make it as a signal of operation, the addition of fine carbon blacks is particularly effective in such a case. In addition, a fine carbon black is in general excellent in retention of a liquid lubricant and contributes to the reduction of a friction coefficient when a lubricant is used in combination. On the other hand, a coarse carbon black having an average particle size of from 230 to 300 nm has a function as a solid lubricant and forms minute protrusions on the surface of the backing layer to reduce the contact area and contributes to the reduction of a friction coefficient.
The specific examples of commercially available fine carbon blacks and coarse carbon blacks which can be used in the present invention are disclosed in WO 98/35345.
When two kinds of carbon blacks respectively having different average particle sizes are used in combination in the backing layer, the proportion of the contents (by mass) of a fine carbon black having a particle size of from 10 to 20 nm and a coarse carbon black having a particle size of from 230 to 300 nm is preferably the former/the latter of from 98/2 to 75/25, more preferably from 95/5 to 85/15.
The content of the carbon black in the back coating layer (the total amount when two kinds of carbon blacks are used) is generally from 30 to 80 mass parts (i.e., weight parts), preferably from 45 to 65 mass parts, based on 100 mass parts of the binder.
It is preferred to use two kinds of inorganic powders respectively having different hardness.
Specifically, a soft inorganic powder having a Mohs"" hardness of from 3 to 4.5 and a hard inorganic powder having a Mohs"" hardness of from 5 to 9 are preferably used in combination.
By the addition of a soft inorganic powder having a Mohs"" hardness of from 3 to 4.5, a friction coefficient can be stabilized against repeating-running. Moreover, a sliding guide pole is not scratched off in hardness within this range. The average particle size of such a soft inorganic powder is preferably from 30 to 50 nm.
The examples of soft inorganic powders having a Mohs"" hardness of from 3 to 4.5 include, e.g., calcium sulfate, calcium carbonate, calcium silicate, barium sulfate, magnesium carbonate, zinc carbonate and zinc oxide. They can be used alone or in combination of two or more.
The content of the soft inorganic powder in a back coating layer is preferably from 10 to 140 mass parts (i.e., weight parts), more preferably from 35 to 100 mass parts, based on 100 mass parts of the carbon black.
By the addition of a hard inorganic powder having a Mohs"" hardness of from 5 to 9, the strength of the back coating layer is increased and running durability is improved. When such hard inorganic powders are used together with carbon blacks and the above-described soft inorganic powders, deterioration due to repeating sliding is reduced and strong back coating layer can be obtained. Appropriate abrasive property is provided to the back coating layer by the addition of the hard inorganic powder and the adhesion of scratched powders to a tape guide pole is reduced. When the hard inorganic powder is used in combination with a soft inorganic powder in particular, sliding characteristics against a guide pole having a rough surface is improved and the stabilization of a friction coefficient of the backing layer can also be brought about.
The average particle size of hard inorganic powders is preferably from 80 to 250 nm, more preferably from 100 to 210 nm.
The examples of hard inorganic powders having a Mohs"" hardness of from 5 to 9 include, e.g., xcex1-iron oxide, xcex1-alumina, and chromium oxide (Cr2O3). These powders may be used alone or in combination. Of the above hard inorganic powders, xcex1-iron oxide and xcex1-alumina are preferred. The content of hard inorganic powders in the backing layer is generally from 3 to 30 mass parts, preferably from 3 to 20 mass parts, based on 100 mass parts of the carbon black.
When the above soft inorganic powder and hard inorganic powder are used in combination in the backing layer, it is preferred to use them selectively such that the difference of hardness between soft and hard inorganic powders is 2 or more, more preferably 2.5 or more, and particularly preferably 3 or more.
It is preferred that the above-described two kinds of inorganic powders respectively having different hardness and specific average particle sizes and the above-described two kinds of carbon blacks respectively having different average particle sizes are contained in the backing layer.
Lubricants may be contained in the backing layer. The lubricants can be arbitrarily selected from among those which can be used in the magnetic layer or the nonmagnetic layer as described above. The content of the lubricant added to the backing layer is generally from 1 to 5 mass parts based on 100 mass parts of the binder.
Support
The support for use in the present invention is preferably a nonmagnetic flexible support, and essentially has a thermal shrinkage factor of preferably 0.5% or less, more preferably 0.2% or less, both at 100xc2x0 C. for 30 minutes and at 80xc2x0 C. for 30 minutes in every in-plane direction of the support. Moreover, the above-described thermal shrinkage factors of the support at 100xc2x0 C. for 30 minutes and at 80xc2x0 C. for 30 minutes are preferably almost equal in every in-plane direction of the support with difference of not more than 10%. The support is preferably a nonmagnetic support. As the nonmagnetic support for use in the present invention, well-known films, such as polyesters (e.g., polyethylene terephthalate and polyethylene naphthalate), polyolefins, cellulose triacetate, polycarbonate, aromatic or aliphatic polyamide, polyimide, polyamideimide, polysulfone, polyaramide, and polybenzoxazole can be used. Highly strong supports such as polyethylene naphthalate or polyamide are preferably used. If necessary, a lamination type support as disclosed in JP-A-3-224127 can be used to vary the surface roughnesses of the magnetic layer surface and the base surface. The support may be previously subjected to surface treatments, such as a corona discharge treatment, a plasma treatment, an easy adhesion treatment, a heat treatment, and a dust removing treatment. Aluminum or glass substrate can also be used as a support in the present invention.
For attaining the object of the present invention, it is necessary to use the support having a central plane average surface roughness (Ra) (defined in JIS B 0601) of 4.0 nm or less, preferably 2.0 nm or less, measured by a surface roughness meter TOPO-3D (a product of WYKO Co.). It is preferred that the support not only has a small central plane average surface roughness but also is free from coarse protrusions having a height of 0.5 xcexcm or more. Surface roughness configuration is freely controlled by the size and the amount of the fillers added to the support. The examples of such fillers include acryl-based organic powders, as well as oxides or carbonates of Ca, Si and Ti. The support for use in the present invention preferably has the maximum height (Rmax) of 1 xcexcm or less, ten point average roughness (Rz) of 0.5 xcexcm or less, central plane peak height (Rp) of 0.5 xcexcm or less, central plane valley depth (Rv) of 0.5 xcexcm or less, central plane area factor (Sr) of from 10% to 90%, and average wavelength (xcexa) of from 5 xcexcm to 300 xcexcm. For obtaining desired electromagnetic characteristics and durability, surface protrusion distribution of the support can be controlled arbitrarily by fillers, e.g., the number of protrusions having sizes of from 0.01 xcexcm to 1 xcexcm can be controlled each within the range of from 0 to 2,000 per 0.1 mm2.
The F-5 value of the support for use in the present invention is preferably from 5 to 50 kg/mm2 (=about 49 to 490 MPa), the thermal shrinkage factor of the support at 100xc2x0 C. for 30 minutes is preferably 3% or less, more preferably 1.5% or less, and the thermal shrinkage factor at 80xc2x0 C. for 30 minutes is preferably 1% or less, more preferably 0.5% or less. The support has a breaking strength of from 5 to 100 kg/mm2 (=about 49 to 980 MPa), an elastic modulus of from 100 to 2,000 kg/mm2 (=about 0.98 to 19.6 GPa), a temperature expansion coefficient of from 10xe2x88x924 to 10xe2x88x928/xc2x0 C., preferably from 10xe2x88x925 to 10xe2x88x926/xc2x0 C., and a humidity expansion coefficient of 10xe2x88x924/RH % or less, preferably 10xe2x88x925/RH % or less. These thermal characteristics, dimensional characteristics and mechanical strength characteristics are preferably almost equal in every in-plane direction of the support with difference of within 10%.
Producing Method
Processes of preparing the magnetic coating solution for use in the magnetic recording medium of the present invention comprises at least a kneading step, a dispersing step and, optionally, blending steps to be carried out before and/or after the kneading and dispersing steps. Any of these respective steps may be composed of two or more separate stages. Materials such as a magnetic powder, a nonmagnetic inorganic powder, a binder, a carbon black, an abrasive, an antistatic agent, a lubricant, a solvent, and the like for use in the present invention may be added at any step at any time. Each material may be added at two or more steps dividedly. For example, polyurethane can be added dividedly at a kneading step, a dispersing step, or a blending step for adjusting viscosity after dispersion. For achieving the object of the present invention, the above steps can be performed partly with conventionally well-known techniques. Powerful kneading machines such as an open kneader, a continuous kneader, a pressure kneader or an extruder are preferably used in a kneading step. When a kneader is used, all or a part of the binder (preferably 30% or more of the total binders) are kneading-treated in the range of from 15 parts to 500 parts per 100 parts of the magnetic powder or nonmagnetic inorganic powder together with a magnetic powder or a nonmagnetic inorganic powder. Details of these kneading are disclosed in JP-A-1-106338 and JP-A-1-79274. When a magnetic layer solution and a nonmagnetic layer solution are dispersed, glass beads can be used, and dispersing media having a high specific gravity, e.g., zirconia beads, titania beads and steel beads are suitable for this purpose. Optimal particle size and packing density of these dispersing media should be selected. Well-known dispersing apparatus can be used in the present invention.
The following methods are preferably used for coating the magnetic recording medium having a multilayer structure in the present invention. As the first method, the lower layer is coated by any of gravure coating, roll coating, blade coating, and extrusion coating apparatus, which are well known in the coating of a magnetic coating solution, and the upper layer is coated while the lower layer is still wet by means of a support pressing type extrusion coating apparatus disclosed in JP-B-1-46186, JP-A-60-238179 and JP-A-2-265672. As the second method, the upper layer and the lower layer are coated almost simultaneously using a coating head equipped with two slits for feeding a coating solution as disclosed in JP-A-63-88080, JP-A-2-17971 and JP-A-2-265672. As the third method, the upper layer and the lower layer are coated almost simultaneously using an extrusion coating apparatus equipped with a backup roll as disclosed in JP-A-2-174965. For preventing the deterioration of the electromagnetic characteristics of the magnetic recording medium due to agglomeration of magnetic powders, it is preferred to impart shear to the coating solution in a coating head by the methods as described in JP-A-62-95174 and JP-A-1-236968. With respect to the viscosity of the coating solution, the range of the numeric values disclosed in JP-A-3-8471 is necessary to be satisfied. For realizing the constitution of the present invention, a successive multilayer coating method in which the magnetic layer is coated on the lower layer after the lower layer has been coated and dried can of course be used without impairing the effect of the present invention. However, for reducing coating defects and improving quality, e.g., free of dropout, it is preferred to use the above simultaneous multilayer coating method.
In the case of a magnetic disc, isotropic orienting property can be sufficiently obtained in some cases without conducting orientation using orientating apparatus, but it is preferred to use well-known random orientation apparatuses, to thereby dispose cobalt magnets diagonally and alternately or apply an alternating current magnetic field using a solenoid. Hexagonal ferrites in general have an inclination for three dimensional random orientation of in-plane and in the vertical direction but it is also possible to make in-plane two dimensional random orientation. Further, it is also possible to impart isotropic magnetic characteristics in the circumferential direction by vertical orientation using well-known methods, e.g., using different pole and counter position magnets. In particular, vertical orientation is preferred when the disc is used in high density recording. Circumferential orientation can be conducted using spin coating.
In the case of a magnetic tape, orientation is done in the machine direction using a cobalt magnet and a solenoid.
In orientation, it is preferred that the drying position of the coated film can be controlled by controlling the temperature and the amount of drying air and coating rate. Coating rate is preferably from 20 to 1,000 m/min. and the temperature of drying air is preferably 60xc2x0 C. or more. Preliminary drying can be performed appropriately before entering the magnet zone.
Use of heat resisting plastic rolls such as epoxy, polyimide, polyamide and polyimideamide, or metal rolls is effective for calendering treatment. It is preferred to use metal rolls for the treatment particularly when magnetic layers are coated on both surfaces of a support. The treatment temperature is preferably 50xc2x0 C. or more, more preferably 100xc2x0 C. or more. The linear pressure is preferably 200 kg/cm (=about 196 kN/m) or more, more preferably 300 kg/cm (=about 294 kN/m) or more.
Physical Properties
The thickness of the magnetic layer in the magnetic recording medium in the present invention is preferably from 0.01 to 0.5 xcexcm, more preferably 0.15 xcexcm or less, and the residual magnetic flux densityxc3x97magnetic layer thickness is preferably from 5 to 200 mTxc2x7xcexcm. The coercive force (Hc) is preferably from 1,800 to 5,000 Oe (=about 144 to 400 kA/m), preferably from 1,800 to 3,000 Oe (=about 144 to 240 kA/m). The distribution of the coercive force is preferably narrow, and SFD (switching field distribution) and SFDr are preferably 0.6 or less.
The squareness ratio of a magnetic disc is from 0.55 to 0.67, preferably from 0.58 to 0.64, in the case of two dimensional random orientation, from 0.45 to 0.55 in the case of three dimensional random orientation, and in the case of vertical orientation, generally 0.6 or more, preferably 0.7 or more in the vertical direction, and when diamagnetic correction is performed, 0.7 or more, preferably 0.8 or more. Orientation ratio of two dimensional random orientation and three-dimensional random orientation is preferably 0.8 or more. In the case of two dimensional random orientation, the squareness ratio in the vertical direction, the Br in the vertical direction, and the Hc in the vertical direction are preferably from 0.1 to 0.5 times of those in the in-plane direction.
In the case of a magnetic tape, the squareness ratio is 0.7 or more, preferably 0.8 or more.
The friction coefficient of the magnetic recording medium according to the present invention against a head at temperature of xe2x88x9210xc2x0 C. to 40xc2x0 C. and humidity of 0% to 95% is 0.5 or less, preferably 0.3 or less, the surface intrinsic resistance of the magnetic surface is preferably from 104 to 1012 xcexa9/sq, the charge potential is preferably from xe2x88x92500 V to +500 V, the elastic modulus at 0.5% elongation of the magnetic layer is preferably from 100 to 2,000 kg/mm2 (=about 980 to 19,600 MPa) in every in-plane direction, the breaking strength is preferably from 10 to 70 kg/mm2 (=about 98 to 686 MPa), the elastic modulus of the magnetic recording medium is preferably from 100 to 1,500 kg/mm2 (=about 980 to 14,700 MPa) in every in-plane direction, the residual elongation is preferably 0.5% or less, and the thermal shrinkage factor at every temperature of 100xc2x0 C. or less is preferably 1% or less, more preferably 0.5% or less, and most preferably 0.1% or less. The glass transition temperature of the magnetic layer (the maximum of elastic modulus loss by dynamic visco-elasticity measurement at 110 Hz) is preferably from 50xc2x0 C. to 120xc2x0 C., and that of the lower layer is preferably from 0xc2x0 C. to 100xc2x0 C. The elastic modulus loss is preferably within the range of from 1xc3x97105 to 8xc3x97108 Pa, and loss tangent is preferably 0.2 or less. If loss tangent is too large, adhesion failure is liable to occur. These thermal and mechanical characteristics are preferably almost equal in every in-plane direction of the medium with difference of within 10%. The residual amount of the solvent in the magnetic layer is preferably 100 mg/m2 or less, more preferably 10 mg/m2 or less. The void ratio of the coated layer is preferably 30% by volume or less, more preferably 20% by volume or less, with both of the lower layer and the upper layer. The void ratio is preferably smaller for obtaining high output but in some cases a specific value should be preferably secured depending on purposes. For example, in a disc-like medium which is repeatedly used, large void ratio contributes to good running durability in many cases.
The magnetic layer has a central plane average surface roughness (Ra) (defined in JIS B 0601) of preferably 5.0 nm or less, more preferably 4.0 nm or less, and especially preferably 3.5 nm or less, measured by a surface roughness meter TOPO-3D (a product of WYKO Co.). The magnetic layer for use in the present invention preferably has the maximum height (Rmax) of 0.5 xcexcm or less, ten point average roughness (Rz) of 0.3 xcexcm or less, central plane peak height (Rp) of 0.3 xcexcm or less, central plane valley depth (Rv) of 0.3 xcexcm or less, central plane area factor (Sr) of from 20% to 80%, and average wavelength (xcexa) of from 5 xcexcm to 300 xcexcm. For obtaining desired electromagnetic characteristics and a friction coefficient, a number of surface protrusions of the magnetic layer surface of sizes (i.e., height) of from 0.01 xcexcm to 1 xcexcm can be controlled arbitrarily within the range of from 0 to 2,000 by controlling the surface property by fillers in the support, the particle size and the amount of the magnetic powders added to the magnetic layer, or by the surface shapes of the rolls of calender treatment. The range of curling is preferably within xc2x13 mm. It can be easily presumed that these physical properties of the magnetic recording medium in the present invention can be varied according to purposes in the lower layer and the upper layer. For example, the elastic modulus of the upper layer is made higher to improve running durability and at the same time the elastic modulus of the lower layer is made lower than that of the upper layer to improve the head touching of the magnetic recording medium.